H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY

H01M8/00—Fuel cells; Manufacture thereof

H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids

H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells

H01M8/04268—Heating of fuel cells during the start-up of the fuel cells

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H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY

H01M8/00—Fuel cells; Manufacture thereof

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H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged

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H01M8/00—Fuel cells; Manufacture thereof

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H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

H01M8/1018—Polymeric electrolyte materials

H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer

H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes

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H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

H01M8/1018—Polymeric electrolyte materials

H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer

H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters

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H01M8/00—Fuel cells; Manufacture thereof

H01M8/10—Fuel cells with solid electrolytes

H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

H01M8/1018—Polymeric electrolyte materials

H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer

H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]

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H01M8/00—Fuel cells; Manufacture thereof

H01M8/10—Fuel cells with solid electrolytes

H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

H01M8/1018—Polymeric electrolyte materials

H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer

H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]

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H01M8/00—Fuel cells; Manufacture thereof

H01M8/10—Fuel cells with solid electrolytes

H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

H01M8/1018—Polymeric electrolyte materials

H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer

H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]

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H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY

H01M8/00—Fuel cells; Manufacture thereof

H01M8/10—Fuel cells with solid electrolytes

H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material

H01M8/1018—Polymeric electrolyte materials

H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer

H01M8/1037—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes

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C08J2343/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Derivatives of such polymers

C08J2343/04—Homopolymers or copolymers of monomers containing silicon

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H01M2300/00—Electrolytes

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H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration

H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02E60/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation

Y02E60/50—Fuel cells

Y02E60/52—Fuel cells characterised by type or design

Y02E60/521—Proton Exchange Membrane Fuel Cells [PEMFC]

Y02E60/522—Direct Alcohol Fuel Cells [DAFC]

Y02E60/523—Direct Methanol Fuel Cells [DMFC]

Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE

Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products

Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Description

Translated from Korean

고분자 전해질막, 이의 제조 방법 및 이를 구비한 연료전지 {Polymer electrolyte membrane, method for preparing the same and fuel cell using the same} A polymer electrolyte membrane, a method for their preparation and a fuel cell {Polymer electrolyte membrane, method for preparing the same and fuel cell using the same} having the same

PEMFC는 소형 및 경량이어도 높은 출력밀도를 구현할 수 있다. PEMFC can implement a high power density may be small and lightweight.더욱이, PEMFC를 사용하면, 발전 시스템의 구성이 간단해진다. Moreover, the use of the PEMFC, the configuration of the power generation system can be simplified.

PEMFC의 기본 구조는 통상적으로, 애노드(연료 전극), 캐소드(산화제 전극), 및 애노드와 캐소드 사이에 배치된 고분자 전해질막을 포함한다. The basic structure of the PEMFC typically comprises an anode (fuel electrode), a cathode (oxidant electrode), and an anode and a polymer electrolyte membrane disposed between the cathode.PEMFC의 애노드에는 연료의 산화를 촉진시키기 위한 촉매층이 구비되어 있으며, PEMFC의 캐소드에는 산화제의 환원을 촉진시키기 위한 촉매층이 구비되어 있다. The anode of the PEMFC has been provided with a catalyst layer to promote oxidation of a fuel and, the cathode of the PEMFC has been provided with a catalyst layer to promote reduction of the oxidant.

PEMFC에 있어서, 고분자 전해질막은, 애노드로부터 캐소드로의 수소이온의 이동을 위한 이온전도체의 역할을 할 뿐만 아니라, 애노드와 캐소드의 기계적 접촉을 차단하는 격리막(separator)의 역할도 한다. In the PEMFC, the polymer electrolyte membrane, as well as the role of an ionic conductor for the migration of hydrogen ions from the anode to the cathode, and also serves as a separator (separator) to block the mechanical contact of the anode and the cathode.따라서, 고분자 전해질막에 대하여 요구되는 특성은, 우수한 이온전도도, 전기화학적 안전성, 높은 기계적 강도, 작동온도에서의 열안정성, 박막화의 용이성 등이다. Accordingly, the characteristics required for the polymer electrolyte membrane, such as a high ionic conductivity, electrochemical safety, high mechanical strength, heat stability, ease of delamination of the operating temperature.

한편, 본 발명을 따르는 폴리실세스퀴옥산기가 도입된 공중합체는, 하기 화학식 1을 가질 수 있다. On the other hand, polysilsesquioxane copolymer introducing group according to an embodiment of the present invention is to may have the formula (I).

한편, 화학식 1 중, a 및 b는 반복 단위의 몰분율로서, 각각, 0.05 내지 0.95, 바람직하게는 0.1 내지 0.9일 수 있으며, a+b=1을 만족한다. On the other hand, in the formula 1, a and b may be in a molar fraction of the repeating unit, respectively, from 0.05 to 0.95, preferably from 0.1 to 0.9, and satisfies a + b = 1.상기 a 및 b를 조절함으로써, 폴리실세스퀴옥산기가 도입된 공중합체의 플렉서블(flexible) 특성을 조절할 수 있다. By controlling the a and b, it can be adjusted by a flexible (flexible) properties of the polysilsesquioxane group is introduced into the copolymer.

한편, 상기 화학식 1을 갖는 폴리실세스퀴옥산기가 도입된 공중합체의 중량 평균 분자량은 1,000-20,000 범위일 수 있다. On the other hand, the weight average molecular weight of the polysilsesquioxane copolymer introducing a group having the Formula 1 may be in the range 1000-20000.

본 발명을 따르는 폴리실세스퀴옥산기가 도입된 공중합체의 일 구현예는 하기 화학식 4 또는 4a를 가질 수 있으나, 이에 한정되는 것은 아니다: One embodiment of the polysilsesquioxane group is introduced into a copolymer according to an embodiment of the present invention, but to have the general formula 4 or 4a, but not limited to:

<화학식 4> <Formula 4>

<화학식 4a> <Formula 4a>

상기 화학식 4 및 4a 중 a 및 b와 상기 화학식 4 및 4a를 갖는 폴리실세스퀴옥산기가 도입된 공중합체의 중량 평균 분자량은 상기 화학식 1에 대하여 기재된 바를 참조한다. The weight average molecular weight of the formula 4 and 4a of the polyester yarn sesquioleate a dioxane group introduced copolymer having the formula 4 and 4a, and a and b are described with respect to the reference bar to the general formula (1).

상기 고분자 전해질막 형성용 조성물 중 용매로는 N-메틸-2-피롤리돈, N, N'-디메틸아세트아미드, 디메틸포름아미드, 메틸설폭사이드, 디메틸설폭사이드 등을 사용할 수 있으나, 이에 한정되지 않는다. As the above polymer electrolyte composition for film formation solvent is N- methyl-2-pyrrolidone, N, N'- dimethylacetamide, dimethylformamide, and the like, but methyl sulfoxide, dimethyl sulfoxide, without limitation no.이들 중 2 이상의 조합을 사용하는 것도 가능하다. It is also possible to use two or more combinations of these.상기 용매의 함량은 고분자 전해질막 형성용 조성물을 기준으로 1중량% 내지 99중량%일 수 있다. The amount of the solvent may be 1% to 99% by weight, based on the composition for forming the polymer electrolyte membrane.상기 용매의 함량이 고분자 전해질막 형성용 조성 물을 기준으로 1중량% 미만일 경우, 고분자 전해질막 형성용 조성물의 코팅성, 점도 등이 저하될 수 있고, 상기 용매의 함량이 고분자 전해질막 형성용 조성물을 기준으로 99중량%를 초과할 경우, 고형분의 함량이 너무 낮아 바람직하지 못하다. When the amount of the solvent is 1% by weight less than the basis of the composition of water for the polymer electrolyte membrane formed polymer electrolyte membrane coating for the composition for forming property, viscosity and the like can be reduced, the composition for the amount of the solvent, the polymer electrolyte membrane formed if it exceeds 99% by weight, based on the undesirable the amount of solid content is too low.

상기 고분자 전해질막 형성용 조성물을 기판 상에 도포한다. The application of the above-mentioned polymer electrolyte film-forming composition on a substrate.이 때 도포방법으로는 특별하게 한정되는 것은 아니며, 스핀 코팅, 바 코팅 등과 같은 공지된 다양한 방법이 이용될 수 있다. At this time it is not applied method is limited, there are known various methods such as spin coating, bar coating can be used.

상기 과정에 따라 얻은 고분자 전해질막은 연료전지의 전해질막으로 사용가능하다. It can be used as the electrolyte membrane of a polymer electrolyte membrane fuel cell obtained according to the process.

본 발명에 따른 고분자 전해질막의 두께는 5 내지 200㎛인 것이 바람직하다. A polymer electrolyte membrane thickness according to the present invention is preferably 5 to 200㎛.만약 고분자 전해질막의 두께가 5㎛ 미만이면 너무 얇아서 찢어질 위험성이 있고, 200㎛를 초과하면 막에 균열이 갈 수가 있어 바람직하지 못하다. If there is the risk of the polymer electrolyte membrane has a thickness less than 5㎛ too thin to tear, it is not preferable to take out the number of cracks in the film when it is more than 200㎛.

또한 일반적으로 상기 금속 촉매로는 담체에 지지된 것이 사용된다. Also in general, the metal catalyst is used it is supported on a carrier.상기 담체로는 아세틸렌 블랙, 흑연과 같은 탄소를 사용할 수도 있고, 알루미나, 실리카 등의 무기물 미립자를 사용할 수도 있다. The carrier may be a carbon, such as acetylene black, graphite, it is also possible to use inorganic fine particles of alumina, silica and the like.담체에 담지된 귀금속을 촉매로 사용하는 경우에는 상용화된 시판되는 것을 사용할 수도 있고, 또한 담체에 귀금속을 담지시켜 제조하여 사용할 수도 있다. When using a noble metal supported on a support as a catalyst may be used include that commercially available, can also be prepared by impregnating a noble metal on a support.

이하, 본 발명을 하기 제조예 및 실시예를 들어 설명하기로 하되, 본 발명이 하기 제조예 및 실시예로 한정되는 것은 아니다. Or less, to the present invention, but will be described for the preparations and examples, to which the present invention is not limited to the preparations and examples.

도 1 내지 도 3에 따르면, 본 발명을 따르는 고분자 전해질막은 온도 또는 습도가 증가할수록 프로톤 전도도가 증가함을 알 수 있다. According to Fig. 1 to Fig. 3, as the present invention, a polymer electrolyte membrane according to the temperature or humidity is increased it can be seen that the proton conductivity is increased.

상기에서 본 발명의 바람직한 제조예를 참조하여 설명하였지만, 해당 기술 분야의 숙련된 당업자는 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다. Has been described with reference to a preferred preparation of the invention in the above, without departing from the spirit and scope of the invention defined in the claims of the skilled in the art is to in the art make various changes and modifications of the invention that will be able to understand.

a 및 b은 몰분율로서, 각각, 0.05 내지 0.95이고, a+b=1이다. a and b is a mole fraction, respectively, from 0.05 to 0.95, and a + b = 1.

제4항에 있어서, 5. The method of claim 4,

상기 화학식 1을 갖는 폴리실세스퀴옥산기가 도입된 공중합체의 중량 평균 분자량이 1,000-20,000인 것을 특징으로 하는 고분자 전해질막. A polymer electrolyte membrane, characterized in that the weight average molecular weight of the polysilsesquioxane group is introduced into the copolymer having the general formula (1) 1000-20000.

상기 폴리실세스퀴옥산기가 도입된 공중합체 중 폴리실세스퀴옥산기의 함량이 폴리실세스퀴옥산기가 도입된 공중합체 100중량부를 기준으로 10중량부 내지 70중량부인 것을 특징으로 하는 고분자 전해질막. The polyester yarn sesquicarbonate of dioxane groups of the copolymer introduced polysilsesquioxane group content of the polysilsesquioxane group introduced a copolymer of 100 parts by weight of a polymer electrolyte, characterized in that 10 parts by weight to 70 parts by weight based on the film of .

캐소드; The cathode;애노드; The anode;및 상기 캐소드와 애노드 사이에 개재된 고분자 전해질막을 구비하되, 상기 고분자 전해질막이 제1항, 제2항 및 제4항 내지 제12항 중 어느 한 항의 고분자 전해질막인 것을 특징으로 하는 연료전지. And, but having a film of a polymer electrolyte interposed between the cathode and the anode, wherein the polymer electrolyte membrane of claim 1, claim 2 and claim 4 to claim 12. A fuel cell according to any one of the characterized in that the polymer electrolyte membrane of the claims.